EP1720700B1 - Couche composee de plastique de base comprenant des nodules de plastique barriere - Google Patents

Couche composee de plastique de base comprenant des nodules de plastique barriere Download PDF

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Publication number
EP1720700B1
EP1720700B1 EP05716747.0A EP05716747A EP1720700B1 EP 1720700 B1 EP1720700 B1 EP 1720700B1 EP 05716747 A EP05716747 A EP 05716747A EP 1720700 B1 EP1720700 B1 EP 1720700B1
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EP
European Patent Office
Prior art keywords
layer
evoh
stream
plastic
equal
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Not-in-force
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EP05716747.0A
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German (de)
English (en)
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EP1720700A1 (fr
Inventor
Jules-Joseph Van Schaftingen
Serge Dupont
Barbara Mabed
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Plastic Omnium Advanced Innovation and Research SA
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Inergy Automotive Systems Research SA
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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B23/00—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose
    • B32B23/04—Layered products comprising a layer of cellulosic plastic substances, i.e. substances obtained by chemical modification of cellulose, e.g. cellulose ethers, cellulose esters, viscose comprising such cellulosic plastic substance as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/0026—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting
    • B29B17/0042—Recovery of plastics or other constituents of waste material containing plastics by agglomeration or compacting for shaping parts, e.g. multilayered parts with at least one layer containing regenerated plastic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/04—Disintegrating plastics, e.g. by milling
    • B29B17/0404—Disintegrating plastics, e.g. by milling to powder
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B17/00—Recovery of plastics or other constituents of waste material containing plastics
    • B29B17/02—Separating plastics from other materials
    • B29B2017/0213—Specific separating techniques
    • B29B2017/0262—Specific separating techniques using electrical caracteristics
    • B29B2017/0265—Electrostatic separation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0012—Combinations of extrusion moulding with other shaping operations combined with shaping by internal pressure generated in the material, e.g. foaming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0017—Combinations of extrusion moulding with other shaping operations combined with blow-moulding or thermoforming
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/02—Combined blow-moulding and manufacture of the preform or the parison
    • B29C49/04—Extrusion blow-moulding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/22—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor using multilayered preforms or parisons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/06—PE, i.e. polyethylene
    • B29K2023/0608—PE, i.e. polyethylene characterised by its density
    • B29K2023/065—HDPE, i.e. high density polyethylene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B29K2023/04—Polymers of ethylene
    • B29K2023/08—Copolymers of ethylene
    • B29K2023/086—EVOH, i.e. ethylene vinyl alcohol copolymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/04—Condition, form or state of moulded material or of the material to be shaped cellular or porous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/26—Scrap or recycled material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7172—Fuel tanks, jerry cans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/52—Mechanical processing of waste for the recovery of materials, e.g. crushing, shredding, separation or disassembly
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/62—Plastics recycling; Rubber recycling
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]

Definitions

  • the present invention relates to a layer made of base plastic comprising barrier plastic nodules and to multilayer structures comprising at least one such layer. It relates more particularly to the recycling and the reuse of the constituents of multilayer hollow bodies comprising at least one barrier plastic layer and one base plastic layer.
  • Such multilayer structures are commonly used in highly varied industries, for example in the manufacture of packaging materials or of fuel tanks.
  • An example of a multilayer fuel tank comprises 5 layers:
  • Patent Application FR 2 765 828 on behalf of the Applicant Company provides a process for the recycling of fuel tanks comprising at least one layer of a base plastic and one layer of a barrier plastic separated by a layer of adhesive plastic, in which the said tanks are reduced to fragments and these fragments are subjected to an electrostatic separation under given conditions.
  • the present invention is based on the surprising observation that, provided that the barrier plastic is distributed in the base plastic in the form of small nodules (with a diameter of less than or equal to one micron), the use of fragments of multilayer structures in monolayer articles or in the external (inner and/or outer) layers of a multilayer structure does not affect its properties.
  • the present invention relates to a layer made of base plastic comprising, in the dispersed form, nodules with a diameter of less than or equal to one micron comprising barrier plastic incompatible with the base plastic.
  • plastic is understood to denote any polymer or blend of polymers. Thermoplastics are highly suitable in the context of the invention.
  • thermoplastic denotes any thermoplastic polymer, including thermoplastic elastomers, and their blends.
  • polymer denotes both homopolymers and copolymers (binary or tertiary in particular). Examples of such copolymers are, without implied limitation: copolymers with a random distribution, sequential copolymers, block copolymers and grafted copolymers.
  • thermoplastic polymer or copolymer with a melting point lower than the decomposition temperature is suitable.
  • Synthetic thermoplastics which exhibit a melting range spread over at least 10 degrees Celsius are particularly highly suitable. Those which exhibit a polydispersion in their molecular mass are examples of such thermoplastics.
  • polyolefins poly(vinyl halide)s
  • thermoplastic polyesters polyketones
  • polyamides polyamides
  • a blend of polymers or copolymers can also be used, as well as a blend of polymers with inorganic, organic and/or natural fillers, such as, for example, but without implied limitation: carbon, salts and other inorganic derivatives, natural fibres, glass fibres and polymer fibres. Good results have also been obtained with nanocomposites (or polymers with fillers of nanometric size).
  • the base plastic is chosen according to the mechanical and/or chemical properties which the structure has to exhibit. To this end, use is generally made of conventional polymers, such as polyolefins or halogenated polymers. Good results have been obtained when the base plastic is essentially composed of one or more polyolefins chosen from ethylene or propylene homopolymers and copolymers.
  • HDPE high density polyethylene
  • barrier plastic (constituting in all or in part the dispersed nodules, it being understood that the barrier plastic can be a blend of barrier plastics and/or can comprise conventional additives, such as pigments, plasticizers, antioxidants, and the like) is understood to denote any plastic incompatible with the base plastic and capable of forming a layer exhibiting a low permeability with regard to specific fluids, such as, for example, hydrocarbon-based fuels.
  • Advantageous crystalline polymers exhibiting such properties are in particular polyamides, fluoropolymers and vinyl alcohol polymers [homopolymers (PVOH) and ethylene-vinyl alcohol copolymers (EVOH)]. Very good results are obtained when the barrier plastic is essentially composed of one or more polymers chosen from polyamides and ethylene-vinyl alcohol copolymers and very particularly of the latter.
  • these nodules or agglomerates of substantially spherical shape, have a diameter (to be understood as meaning the mean diameter, regarded as being the mean of the greatest dimension of the substantially spherical agglomerates) of less than or equal to 1 micron, preferably of less than or equal to 0.8 ⁇ m, indeed even of less than or equal to 0.5 ⁇ m.
  • the diameter of these nodules is generally greater than or equal to 0.1 ⁇ m, indeed even greater than or equal to 0.2 ⁇ m.
  • the layer made of base plastic comprising nodules in accordance with the invention can be a monolayer article, such as a film, a sheet, a hollow body (container) and the like. However, advantageously, it is a layer within a multilayer structure.
  • the term "multilayer structure" according to this alternative form of the invention is understood to mean any article having at least two layers, including one essentially composed of base plastic with nodules of barrier plastic.
  • this article is a hollow body intended to contain a powder, granules, and the like, and preferably a fluid.
  • the multilayer structure also comprises a layer essentially composed of a plastic which is a barrier to the migration of the fluid which it contains and/or of certain gases (air, water vapour).
  • the base plastic layer which comprises nodules is an external layer (either the inner layer of the hollow body, in contact with the fluid, or the outer layer, in contact with the outside world), referred to hereinafter as "layer B".
  • layer B is the inner layer of the hollow body.
  • barrier plastic in this layer B is generally less than 5 % by weight. In practice, this content is generally less than 1 %, indeed even less than 0.5 %.
  • the multilayer hollow body in accordance with this alternative form of the invention can be used in many different applications, in particular for the purpose of transporting or containing various types of fluid, in the form of a pipe or container, such as a bottle or tank. It can be used in particular in the field of motor vehicles, in particular in the form of a fuel tank or of a filler neck for a fuel tank. Excellent results have been obtained in the case of a fuel tank.
  • the multilayer structure according to this alternative form of the invention is a fuel tank, it preferably comprises at least one layer essentially composed of EVOH (ethylene-vinyl alcohol copolymer) and one layer essentially composed of HDPE (high density polyethylene) comprising EVOH nodules with a diameter of less than or equal to 1 ⁇ m.
  • EVOH ethylene-vinyl alcohol copolymer
  • HDPE high density polyethylene
  • the barrier plastic used in some alternative forms of the invention often exhibits poor adhesion with regard to the conventional polymers of which the base plastic layer is generally essentially composed, which often compels that recourse be had to an adhesive plastic layer between the barrier layer and the base layer of the structure according to the invention.
  • the adhesive plastic according to this alternative form of the invention is chosen according to the nature of the barrier plastic and of the base plastic. Use is frequently made, as adhesive plastic, of a compatibilized polyolefin and in particular of compatibilized polyethylene.
  • the compatibilization can be obtained in particular by a grafting, in particular using a carboxylic acid anhydride, for example maleic anhydride.
  • the adhesive plastic is preferably essentially composed of a polyolefin grafted with maleic anhydride, in particular of polyethylene grafted with maleic anhydride.
  • the adhesive layer is generally thin with respect to the combined structure and in particular it does not exceed a few % of the general thickness of the structure.
  • the barrier layer can either be one of the two external layers (situated on either side of the structure) or can be an intermediate layer included between the two external layers.
  • the latter alternative form is advantageous, the barrier plastic often being weaker than the base plastic.
  • the barrier plastic layer is sandwiched between two base plastic layers, there are generally two layers of adhesive (one on each side of the barrier layer), each having a thickness of the order of 1 to 2 %, indeed even 3 %, of the structure.
  • the overall content of adhesive in the structure generally does not exceed 10 %, preferably 8 %, indeed even 5 %, by weight of the overall structure.
  • the base plastic layer or layers comprising barrier plastic in the dispersed form to comprise production scraps with similar structures (that is to say, having a barrier plastic layer and a base plastic layer comprising or not comprising dispersed barrier plastic) or fragments of waste similar structures optionally subjected to a pretreatment (in particular for the purpose of purifying them).
  • the structure according to the invention comprises at least one second base plastic layer comprising barrier plastic dispersed in the form of nodules with a diameter of less than or equal to one micron and this second layer is an intermediate layer (inserted between 2 layers) of the hollow body (layer C).
  • Its content of barrier plastic is also less than 15 % by weight, preferably less than or equal to 8 % by weight and in a very particularly preferred way less than or equal to 5 % by weight.
  • this content will advantageously be greater than the content of barrier plastic in the inner layer and, in a particularly preferred way, greater than or equal to 1 % by weight, indeed even greater than or equal to 2 % by weight.
  • This alternative form of the invention is advantageous as it offers the possibility of using a greater amount of recycled plastic (production scraps or waste former structures).
  • a good compromise (economic advantage/mechanical properties) is obtained when the content of barrier plastic in this intermediate layer is from 1 to 8 % by weight. This is because, above 8 % by weight of barrier plastic, the mechanical properties (and in particular the cold impact strength) of the multilayer structures become inadequate for certain applications.
  • the present invention relates to a multilayer structure having at least two base plastic layers (one external (B) and one intermediate (C)) with dispersed barrier plastic, the content of barrier plastic in the layer B being less than 1 % by weight and the content of barrier plastic in the layer C being from 1 to 8 % by weight.
  • the layer and/or the multilayer structure according to the invention can be prepared in any known way, generally by extrusion, injection moulding, slush moulding, thermoforming, and the like. In particular, this layer can be prepared by extrusion.
  • moulding processes are highly suitable and in particular the process referred to as extrusion-blow moulding.
  • the present invention also relates to a process for the manufacture of a hollow body as described above, the said process comprising at least one stage of extrusion-blow moulding of a multilayer parison comprising at least one layer of a base plastic comprising barrier plastic dispersed in the form of nodules with a diameter of less than or equal to one micron.
  • this layer is an external layer of the parison and, in a very particularly preferred way, the parison also comprises a barrier plastic layer.
  • the layers of the abovementioned parison can have any relative thickness.
  • the barrier plastic layer is generally limited to a few % only (typically between 1 and 5 %, indeed even between 2 and 4 %, by weight of the structure), the remainder of the structure being generally essentially composed of base plastic (the optional adhesives also being used in the proportion of a few % only).
  • the dispersing of the barrier plastic in the base plastic can be carried out during the processing by extrusion-blow moulding.
  • this dispersing is sometimes difficult to carry out by varying the processing parameters alone, even using compatibilizing agents (for example of similar nature to the abovementioned adhesives) and/or appropriate mixing devices (mixer nozzles, static mixers).
  • compatibilizing agents for example of similar nature to the abovementioned adhesives
  • mixing devices mixer nozzles, static mixers.
  • the Applicant Company has found that, surprisingly, when the said layer comprises fragments of a similar multilayer structure which have been subjected beforehand to an electrostatic separation treatment, this dispersing was carried out without difficulty, this being the case even in the absence of the abovementioned compatibilizing agents and/or abovementioned mixing devices.
  • an advantageous alternative form of this aspect of the invention consists of a manufacturing process as described above but incorporating a process for recycling at least a portion of a multilayer hollow body comprising at least one barrier plastic layer and one base plastic layer and comprising the following stages :
  • the stream (A) it is advantageous for the stream (A) to have a content of barrier plastic of less than 1 % by weight and for the stream (B) to have a content of barrier plastic of greater than or equal to 1 % by weight.
  • the fragments resulting from the stream (A) can be used as is, as external layer, or can be blended with optional additives, reinforcements, and the like, and/or with virgin base plastic (not yet used).
  • virgin base plastic not yet used.
  • the latter alternative form (diluting with virgin plastic) is preferred.
  • a degree of dilution of greater than or equal to 20 %, and even of greater than or equal to 30 %, but less than or equal to 80 %, indeed even less than or equal to 60 %, is highly suitable [the term "degree of dilution" is understood to mean the % by weight of fragments with respect to the (fragments + virgin resin) blend].
  • the stream (B) is used in an intermediate layer of the parison. It can be used as is or diluted with virgin plastic. Generally, it is possible to use material resulting from this stream as is, provided that its content of barrier plastic is not excessively high. In the case in particular of multilayer fuel tanks, it has been found that a content of less than or equal to 8 % by weight gives good results. Consequently, according to an advantageous alternative from, in the process described above, the stream (B) has a content of barrier plastic of less than or equal to 8 % by weight and the parison comprises an intermediate layer based on fragments resulting from this stream (B).
  • the fragmentation can be carried out in any known way, at ambient temperature or under hot conditions. It can, for example, be carried out between the crystallization temperature of the barrier plastic (Tc, in °C) and Tc - 20°C, as disclosed in the abovementioned Patent Application FR 2 765 828 . In the case of recycling of production scraps, it is advantageous to fragment them in line when they are still hot.
  • fragments having their greatest dimension of greater than or equal to 1 mm, preferably of greater than or equal to 2 mm, indeed even of greater than or equal to 5 mm, are preferably present.
  • this dimension is less than or equal to 15 mm, preferably less than or equal to 12 mm, indeed even less than or equal to 8 mm.
  • the electrostatic separation can also be carried out in any known way, devices being available commercially for this purpose. It is preferably carried out using equipment in which the fragments are first charged and subsequently separated into streams of different composition by passing through an electrostatic field and collecting by means of an appropriate device.
  • the latter advantageously comprises at least two separate containers (or separate compartments in the same container), so as to be able to separately collect the abovementioned streams (A) and (B). It may sometimes prove to be advantageous to collect at least three separate streams, each having a different content of barrier plastic.
  • the stream poorest in barrier plastic corresponds to the stream (A), the stream with an average content to the stream (B) and the stream having the highest content (typically greater than or equal to 10 %, indeed even greater than or equal to 20 %, by weight) to a stream (C).
  • the content of barrier plastic in this stream (C) will generally be less than or equal to 50 %, preferably less than or equal to 40 %, indeed even less than or equal to 30 %.
  • This stream (C) will preferably not be reused as is in a new multilayer structure, its composition generally not making it possible to obtain good mechanical properties.
  • This stream will generally be discarded or, advantageously, taking into account the cost of barrier plastics in general, will be subjected to one or more appropriate treatments which make it possible to enrich it in barrier plastic and, doing this, to recycle it in the barrier layer of a multilayer structure (similar to or different from the original structure).
  • At least one third stream (C) is generated, the content of barrier plastic of which is greater than or equal to 10 %, and this stream (C) is subjected to a subsequent treatment stage which makes it possible to enrich it in barrier plastic.
  • a treatment stage can consist of a selective dissolution of the barrier plastic and a reprecipitation of the latter, as disclosed in Patent Application FR 03/03209 .
  • Such waste tanks or their production scraps advantageously act as base for the manufacture of new tanks according to the present invention.
  • some manufacturing operations for example, during (re)start-up
  • will be carried out without use of production scraps whereas others will use it to a greater or lesser extent, depending on the quality of the preceding production operations.
  • Some production operations can also be carried out based on plastics resulting from waste tanks. In this case, these plastics will preferably have been subjected to a purification (in particular purification from residual fuel) and/or regeneration treatment (it being understood that the waste plastics, and in particular the HDPE, may have deteriorated as a result of the ageing thereof).
  • a regenerating agent such as a polyfunctional epoxide
  • the waste base plastic in particular when it is HDPE
  • the thickness of the intermediate layer of regrind can range up to 50 % of the total thickness of the structure, whereas, in the fuel tanks according to the prior art, where regrind was recycled as is, without electrostatic separation, this thickness was generally limited to 40 % of the total thickness of the structure, in order not to place an excessive strain on its properties.
  • the Applicant Company has found that, in the layers of regrind not subjected to an electrostatic separation, the barrier plastic nodules generally had a diameter of greater than or equal to 1 ⁇ m, indeed even of greater than or equal to 2 ⁇ m, in contrast to the structures of the present invention, where the nodules are less than 1 ⁇ m.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Laminated Bodies (AREA)
  • Blow-Moulding Or Thermoforming Of Plastics Or The Like (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Wrappers (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Claims (12)

  1. Couche faite de HDPE (polyéthylène haute densité) comprenant, sous forme dispersée, des nodules ayant un diamètre inférieur ou égal à un micromètre comprenant de l'EVOH (copolymère d'éthylène/alcool vinylique).
  2. Structure multicouche comprenant au moins une couche selon la revendication précédente.
  3. Structure multicouche selon la revendication précédente, caractérisée en ce que la couche de HDPE qui comprend des nodules est une couche externe (intérieure ou extérieure) de la structure multicouche (couche B).
  4. Structure multicouche selon la revendication 3, caractérisée en ce qu'elle est essentiellement composée d'un corps creux destiné à contenir un fluide et en ce que la couche B est la couche intérieure du corps creux en contact avec le fluide.
  5. Structure multicouche selon la revendication 3 ou 4, caractérisée en ce qu'elle comprend au moins une deuxième couche de HDPE comprenant, sous forme dispersée, des nodules ayant un diamètre inférieur ou égal à un micromètre comprenant de l'EVOH.
  6. Structure multicouche selon la revendication précédente, caractérisée en ce que la couche C est une couche intermédiaire de la structure.
  7. Structure multicouche selon la revendication précédente, caractérisée en ce que la teneur en EVOH dans la couche B est inférieure à 1 % en poids et en ce que la teneur en EVOH dans la couche C est de 1 à 8 % en poids.
  8. Procédé pour la fabrication d'une couche selon la revendication 1 ou d'une structure multicouche selon l'une quelconque des revendications 2 à 7, caractérisé en ce qu'il comprend au moins une étape de moulage par extrusion-soufflage d'une paraison multicouche comprenant au moins une couche externe de HDPE comprenant, sous forme dispersée, des nodules ayant un diamètre inférieur ou égal à un micromètre comprenant de l'EVOH.
  9. Procédé selon la revendication précédente, caractérisé en ce qu'il incorpore un procédé pour recycler au moins une partie d'un corps creux multicouche comprenant au moins une couche d'EVOH et une couche de HDPE et en ce qu'il comprend les étapes suivantes :
    - ladite partie du corps creux est fragmentée ;
    - les fragments obtenus sont soumis à au moins une étape de séparation électrostatique, de façon que soient obtenus au moins un courant (A) de fragments pauvres en EVOH et un courant (B) de fragments plus riches en EVOH ;
    - une paraison multicouche, ayant une couche externe comprenant des fragments résultant du courant (A), est fabriquée par extrusion ;
    - ladite paraison est moulée par soufflage.
  10. Procédé selon la revendication précédente, caractérisé en ce que le courant (A) a une teneur en EVOH inférieure à 1 % en poids et le courant (B) a une teneur en EVOH égale ou supérieure à 1 % en poids.
  11. Procédé selon la revendication précédente, caractérisé en ce que le courant (B) a une teneur en EVOH inférieure ou égale à 8 % en poids et en ce que la paraison comprend une couche intermédiaire à base de fragments résultant de ce courant (B).
  12. Procédé selon l'une quelconque des revendications 9 à 11, caractérisé en ce que, durant la séparation électrostatique, au moins un troisième courant (C) est généré, ayant une teneur en EVOH égale ou supérieure à 10 %, et en ce que ce courant (C) est soumis à une étape de traitement supplémentaire qui rend possible son enrichissement en EVOH.
EP05716747.0A 2004-02-26 2005-02-21 Couche composee de plastique de base comprenant des nodules de plastique barriere Not-in-force EP1720700B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0401946A FR2866828B1 (fr) 2004-02-26 2004-02-26 Couche en matiere plastique de base comprenant des nodules de matiere plastique barriere
PCT/EP2005/050730 WO2005082615A1 (fr) 2004-02-26 2005-02-21 Couche composee de plastique de base comprenant des nodules de plastique barriere

Publications (2)

Publication Number Publication Date
EP1720700A1 EP1720700A1 (fr) 2006-11-15
EP1720700B1 true EP1720700B1 (fr) 2016-09-21

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EP05716747.0A Not-in-force EP1720700B1 (fr) 2004-02-26 2005-02-21 Couche composee de plastique de base comprenant des nodules de plastique barriere

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US (1) US7858016B2 (fr)
EP (1) EP1720700B1 (fr)
JP (2) JP4976275B2 (fr)
KR (2) KR101330496B1 (fr)
CN (1) CN100534784C (fr)
BR (1) BRPI0507924A (fr)
FR (1) FR2866828B1 (fr)
WO (1) WO2005082615A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2965757A1 (fr) * 2010-10-08 2012-04-13 Inergy Automotive Systems Res Reservoir a carburant en matiere plastique
US9597848B1 (en) 2012-05-25 2017-03-21 Robertson Fuel Systems Llc Method and system for forming a self-sealing volume
US9802476B1 (en) 2012-05-25 2017-10-31 Robertson Fuel Systems, Llc Method and system for forming a self-sealing volume using a breather system
US10471676B1 (en) 2013-03-12 2019-11-12 Robertson Fuel Systems, L.L.C. Method and system for forming a self-sealing volume with an aqueous polyurethane dispersion layer
EP2783829B1 (fr) * 2013-03-29 2016-10-19 Inergy Automotive Systems Research (Société Anonyme) Procédé de fabrication d'un corps creux
EP3459709A1 (fr) * 2017-09-26 2019-03-27 Magna Steyr Fuel Systems GesmbH Réservoir en matière plastique

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Publication number Publication date
FR2866828A1 (fr) 2005-09-02
JP4976275B2 (ja) 2012-07-18
JP2007528307A (ja) 2007-10-11
JP5662292B2 (ja) 2015-01-28
JP2012061859A (ja) 2012-03-29
FR2866828B1 (fr) 2006-07-07
WO2005082615A1 (fr) 2005-09-09
KR20060134084A (ko) 2006-12-27
CN1925983A (zh) 2007-03-07
KR101330496B1 (ko) 2013-11-15
US7858016B2 (en) 2010-12-28
KR20130004531A (ko) 2013-01-10
US20070184224A1 (en) 2007-08-09
BRPI0507924A (pt) 2007-07-17
EP1720700A1 (fr) 2006-11-15
CN100534784C (zh) 2009-09-02

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